Supporting Information:
Photoinduced Fe-based Atom Transfer Radical Polymerization in the
Absence of Additional Ligands, Reducing Agents and Radical Initiators
Xiangcheng Pan, Nikhil Malhotra, Jianan Zhang, Krzysztof Matyjaszewski*
Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh,
Pennsylvania 15213, United States
*Corresponding author, E-mail: (K. M.) [email protected].
1 Additional data.
Light source
Table S1. Results of photoinduced Fe-catalyzed ATRP of methacrylates under different
light sources. Conditions: [MMA]:[EBPA]:[FeBr3] = 100:1:1, 33.3% MeCN, hν
Entry
1
2
3
4
5
Irradiation source
4.9 mW/cm2 UV
2.1 mW/cm2 UV
0.9 mW/cm2 392 nm
No light
No light, heat at 60 °C
Time
24 h
24 h
22 h
120 h
24 h
Conv.
50%
6%
7%
0%
0%
Mn,th
5200
840
940
-
Mn,GPC
4300
1080
1000
-
Mw/Mn
1.18
1.20
1.13
-
Amount of Fe
Table S2. Results of photoinduced Fe-catalyzed ATRP of methacrylates under different
amounts of Fe catalysts. Conditions: [MMA]:[EBrPA]:[FeBr3] = 100:1:x, and 392 nm
33.3 % MeCN. Entry
Amount of FeBr3
Time Conv. Mn,th Mn,GPC Mw/Mn
1
0 equiv
18 h
9%
900 1.31e5 2.03
2
10 mol%
18 h 39% 3900 4400
1.63
3
10 mol%
30 h 59% 5900 6200
1.51
4
10 mol%
45 h 76% 7600 7800
1.39
5
20 mol%
30 h 18% 1800 2700
1.39
6
20 mol%
45 h 58% 4100 6300
1.37
7
1 equiv (100 mol%)
68 h 41% 4100 5000
1.21
8
1 equiv + 1 eq TBABr 68 h
0%
9
1 equiv w/o hv
41 h
0%
a
0 equiv
4h
10% 1000 2.52e5 2.49
10
a) 4.9 mW/cm2 365 nm irradiation source used.
2 Solvent
Table S3. Results of photoinduced Fe-catalyzed ATRP of methacrylates in different
solvents. Conditions: [MMA]:[EBrPA]:[FeBr3] = 100:1:1, and 4.9 mW/cm2 UV, 33.3 %
solvent. Entry
1
2
3
4
5
6
solvent
MeCN
MeCN (16%)
MeCN (50%)
DMF
Anisole
None
Time
24 h
24 h
24 h
24 h
24 h
24 h
Conv.
50%
24%
33%
35%
0%
0%
Mn,th
5200
2600
3500
3700
-
Mn,GPC
4300
2300
3000
4800
-
Mw/Mn
1.18
1.21
1.28
1.45
-
Evolution of GPC traces of chain-extension of PMMA-Br with BA
[BA]0: [PMMA -Br]0 : [CuBr2]0 : [CuBr]0 : [PMDETA]0 = 400 : 1 : 0. 1 : 0.9 : 1.0;
anisole: 30 vol%, DMF: 2.5wt%; total volume = 5.0 mL, temp. = 70 °C.
Figure S1. Evolution of GPC traces with time for chain extension with BA from
macroinitiator PMMA-Br.
3 Evolution of GPC traces of chain-extension of PMMA-Br with St
[St]0: [PMMA -Br]0 : [CuBr2]0 : [Sn(EH)2]0 : [TPMA]0 = 400 : 1 : 0. 03 : 0.015 : 0.15;
anisole: 40 vol%, DMF: 2.5wt%; total volume = 5.25 mL, temp. = 60 °C.
Figure S2. Evolution of GPC traces with time for chain extension with St from
macroinitiator PMMA-Br.
Figure S3. UV-vis spectra of FeBr2 (0.3 mM), FeBr3 (0.3 mM), and EBPA (0.3 mM) in
MMA/MeCN (2:1, v/v) solution.
4